Preparation and characterization of a new sustainable bio-based elastomer nanocomposites containing poly(glycerol sebacate citrate)/chitosan/n-hydroxyapatite for promising tissue engineering applications.

Poly (glycerol sebacate citrate) (PGSC) has potential applications in tissue engineering due to its biodegradability and suitable elasticity. However, its applications are restricted owing to its acidity and high degradation rate. In this study, a new bio-nanocomposite based on PGSC has been synthesized by incorporating chitosan (CS) and various concentrations of hydroxyapatite nanoparticles (n-HA). It is assumed that the basicity of a CS and hydroxyl groups of n-HA will reduce the acidity of PGSC and control the rate of degradation. Also, the biocompatibility of n-HA and inherent hydrophilicity of CS can improve cell adhesion and proliferation of PGSC-based scaffolds. FTIR, XRD, FESEM, and EDX tests confirmed the synthesis of these nanocomposites and the interaction between each of the components. The results of the DMTA test also indicated the elastic behavior of the samples embedded with n-HA. The hydrophilicity assay demonstrated that the water contact angle of the scaffolds decreased as the concentration of n-HA augmented, and it reached the value of 44 ± 0.9° for nanocomposite containing 5 wt.% n-HA. The degradation rate of all PGSC nanocomposites was reduced due to the anionic groups of n-HA and CS. TGA assay indicated that the incorporation of n-HA led to the enhancement of scaffolds' thermal stability. Furthermore, the synergistic effect of CS and n-HA on the enhancement of protein adsorption and cell proliferation was confirmed through protein adhesion and MTT assay, respectively. Consequently, the addition of n-HA and CS perform the new bio-nanocomposites scaffolds based on PGSC with sufficient hydrophilicity, flexibility, and thermal stability in tissue engineering applications.

Preparation and properties investigation of biodegradable poly (glycerol sebacate-co-gelatin) containing nanoclay and graphene oxide for soft tissue engineering applications.

This study has attempted to systematically investigate the influence of nanoclay and graphene oxide (GO) on thermal, mechanical, hydrophobic, and, most importantly, biological properties of poly(glycerol sebacate)/gelatin (PGS/gel) nanocomposites. The PGS/gel copolymer nanocomposites were successfully synthesized via in situ polymerization, approved by rudimentary characterization methods. The nanofillers were appropriately dispersed within the elastomeric matrix according to morphological studies. Also, the fillers posed as a hydrophobic entity that slightly decreased the hydrophilic properties of PGS/gel. This could be sensed clearly in hybrid composite due to the robust network of GO and clay. Water contact angle values for gelatin-contained nanocomposites were reported in the range of 38.42° to 66.7°, indicating the hydrophilic nature of the prepared samples. Thermal and mechanical studies of nanocomposites displayed rather contradicting results as the former improved while a slight decrease in the latter was noticed compared to the pristine specimens. In dry conditions, their storage modulus was in the range of 0.94-6.4 MPa, making them suitable for mimicking some soft tissues. The swelling ratio for nanocomposites containing nanoparticles was associated with an ascending trend so that GO improved the swelling rate by up to 45%. Biological analyses, such as Ames and in vitro cell viability tests, exhibited promising outcomes. As for the mutagenesis effect, the PGS and hybrid samples showed negative results. The presence of functional groups on the nanofillers' surface positively influenced the cells' metabolic activity as well as its attachment to the matrix. After 7 days, the cell proliferation rate resulted in an 82% improvement for the GO-containing nanocomposite, significantly higher than its neat counterpart (65%). This study has shown the feasibility of the prepared bio-elastomer nanocomposites for diverse tissue engineering applications.

In-Out Surface Modification of Halloysite Nanotubes (HNTs) for Excellent Cure of Epoxy: Chemistry and Kinetics Modeling.

In-out surface modification of halloysite nanotubes (HNTs) has been successfully performed by taking advantage of 8-hydroxyquinolines in the lumen of HNTs and precisely synthesized aniline oligomers (AO) of different lengths (tri- and pentamer) anchored on the external surface of the HNTs. Several analyses, including FTIR, H-NMR, TGA, UV-visible spectroscopy, and SEM, were used to establish the nature of the HNTs' surface engineering. Nanoparticles were incorporated into epoxy resin at 0.1 wt.% loading for investigation of the contribution of surface chemistry to epoxy cure behavior and kinetics. Nonisothermal differential scanning calorimetry (DSC) data were fed into home-written MATLAB codes, and isoconversional approaches were used to determine the apparent activation energy (Eα) as a function of the extent of cure reaction (α). Compared to pristine HNTs, AO-HNTs facilitated the densification of an epoxy network. Pentamer AO-HNTs with longer arms promoted an Excellent cure; with an Eα value that was 14% lower in the presence of this additive than for neat epoxy, demonstrating an enhanced cross-linking. The model also predicted a triplet of cure (m, n, and ln A) for autocatalytic reaction order, non-catalytic reaction order, and pre-exponential factor, respectively, by the Arrhenius equation. The enhanced autocatalytic reaction in AO-HNTs/epoxy was reflected in a significant rise in the value of m, from 0.11 to 0.28. Kinetic models reliably predict the cure footprint suggested by DSC measurements.

Electrically conductive biocompatible composite aerogel based on nanofibrillated template of bacterial cellulose/polyaniline/nano-clay.

Bacterial cellulose (BC) aerogel owing to its porous and 3D structure, poses a suitable matrix for embedding nanomaterials and polymers. Herein, BC composites comprising nano-clay/polyaniline (PANI) were synthesized via a two-step procedure. Clay nanoplatelets were dispersed in the BC membrane to form a nanofibrillated template for aniline in-situ polymerization leading to formation of a double interconnected network of electrically conductive path within the aerogel. Deposition of PANI particles on BC/clay nanocomposite was confirmed by FTIR, XRD, FESEM, and EDX techniques. The surface electrical conductivity of 0.49 S/cm was obtained for the composite aerogel comprising 5 wt% nano-clay which is 16 folds higher than that of the sample without nano-clay. Thermal stability and storage modulus of the aerogels was improved by inclusion of PANI and nano-clay. Synergistic effect of clay and polyaniline on biocompatibility and cell adhesion was obtained with no mutagenic or carcinogenic effects. The developed electrically conductive composite aerogels can be utilized as suitable scaffolds for tissue engineering applications demanding a good balance of flexibility, dimensional and thermal stability and biocompatibility.

Review of Bioprinting in Regenerative Medicine: Naturally Derived Bioinks and Stem Cells.

Regenerative medicine offers the potential to repair or substitute defective tissues by constructing active tissues to address the scarcity and demands for transplantation. The method of forming 3D constructs made up of biomaterials, cells, and biomolecules is called bioprinting. Bioprinting of stem cells provides the ability to reliably recreate tissues, organs, and microenvironments to be used in regenerative medicine. 3D bioprinting is a technique that uses several biomaterials and cells to tailor a structure with clinically relevant geometries and sizes. This technique's promise is demonstrated by 3D bioprinted tissues, including skin, bone, cartilage, and cardiovascular, corneal, hepatic, and adipose tissues. Several bioprinting methods have been combined with stem cells to effectively produce tissue models, including adult stem cells, embryonic stem cells (ESCs), induced pluripotent stem cells (iPSCs), and differentiation techniques. In this review, technological challenges of printed stem cells using prevalent naturally derived bioinks (e.g., carbohydrate polymers and protein-based polymers, peptides, and decellularized extracellular matrix), recent advancements, leading companies, and clinical trials in the field of 3D bioprinting are delineated.

Fabricating an electroactive injectable hydrogel based on pluronic-chitosan/aniline-pentamer containing angiogenic factor for functional repair of the hippocampus ischemia rat model.

The hippocampus, a critical cerebral region involved in learning and memory formation, is especially vulnerable to ischemic defect. Here, we developed an injectable electroactive hydrogel based on pluronic-chitosan/aniline-pentamer with proper conductivity around 10-4 S/cm to achieve the functional repair of the hippocampus following the ischemic defect. FTIR, DSC, and TGA measurements were performed to assess the chemical structure and thermal stability of the synthesized hydrogel. Aniline pentamer decreased the swelling capacity, degradation, and drug release rate. Further, contact angle, melting point, and gelation time of hydrogels were enhanced by addition of aniline oligomer. Moreover, it endowed the on-demand electro-responsive drug release. Injectability of hydrogel was evaluated by rheometry, exhibiting proper gelling time at the body temperature. The ionic/electrical conductivity and desired in vitro biocompatibility with PC12 cells were also achieved. Injection of VEGF-loaded electroactive hydrogel in the hippocampal ischemic animal model resulted in decreased infarction volume, improved hippocampal dependent learning, and memory performance. Taken all together, the results confirmed that fabricated injectable hydrogel would be a suitable candidate for ischemic defect treatment and can lead to new horizons to treat neurological disorders.

Electroactive poly (p-phenylene sulfide)/r-graphene oxide/chitosan as a novel potential candidate for tissue engineering.

Designing novel biomaterials for tissue engineering purpose is an obvious necessary considering ever increasing need for appropriate biocompatibility and properties to achieve the maximum regeneration. In this research, a new type of biomaterial based on poly (phenylene sulfide) (PPS) and reduced graphene oxide (rGO) was synthesized and applied within chitosan based hydrogel to evaluate its performance as a wound dressing potentially. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction spectrometry (XRD), scanning electron microscopy (SEM) and compression tests were performed to assess suitability of composite biomaterial. Thermal behavior of the PPS/rGO composite was evaluated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The PPS/rGO composition of 90: 10 (w/w) was selected because of having the highest biocompatibility and utilized in chitosan hydrogel. Chitosan hydrogel swelling ratio was declined from 800 to 200% by PPS/rGO addition; likewise, water vapor transition rate (WVTR) was dropped. A proper biocompatibility and cell attachment was confirmed, where porosity of ca. 80% appeared promising for tissue engineering uses. Overall, the result confirmed the appropriateness of PPS/rGO for tissue engineering uses.

Chitosan in Biomedical Engineering: A Critical Review.

Biomedical engineering seeks to enhance the quality of life by developing advanced materials and technologies. Chitosan-based biomaterials have attracted significant attention because of having unique chemical structures with desired biocompatibility and biodegradability, which play different roles in membranes, sponges and scaffolds, along with promising biological properties such as biocompatibility, biodegradability and non-toxicity. Therefore, chitosan derivatives have been widely used in a vast variety of uses, chiefly pharmaceuticals and biomedical engineering. It is attempted here to draw a comprehensive overview of chitosan emerging applications in medicine, tissue engineering, drug delivery, gene therapy, cancer therapy, ophthalmology, dentistry, bio-imaging, bio-sensing and diagnosis. The use of Stem Cells (SCs) has given an interesting feature to the use of chitosan so that regenerative medicine and therapeutic methods have benefited from chitosan-based platforms. Plenty of the most recent discussions with stimulating ideas in this field are covered that could hopefully serve as hints for more developed works in biomedical engineering.

Correlation of Microstructure, Rheological and Morphological Characteristics of Synthesized Polypropylene (PP) Reactor Blends Using Homogeneous Binary Metallocene Catalyst.

A novel binary homogeneous catalyst system based on (I): rac-Me2Si(2-Me-4-PhIn)2ZrCl2 and (II): (2-PhIn)2ZrCl2 catalysts at various molar ratios was utilized for the synthesis of polypropylene (PP) reactor blends with bimodal molecular weight distribution (MWD). The results of gel permeation chromatography analyses revealed that the catalyst (I) was responsible for the production of i-PP with high molecular weight (MW) while the individual use of catalyst (II) led to the production of an elastomeric PP with relatively low MW. However, application of the binary catalyst system led to high MW bimodal MWD products being highly dependent on the catalysts' molar ratios. Increasing the molar ratio of catalyst (II) to catalyst (I) resulted in a notable enhancement of the products' complex viscosity due to the increased MW, a higher level of chains' entanglements and formation of amorphous blocks along the polymer chains. All products exhibited a single relaxation that shifted towards longer times upon changing the catalysts' molar ratios. Scanning electron microscopy results revealed that the fracture surface of the blends, synthesized by the binary catalyst system, became more heterogeneous in comparison with the products obtained by the individual use of the catalyst (I). The observed heterogeneity was found to increase by increasing the amount of catalyst (II). Such morphological change was further corroborated by the dynamic rheological data, indicating a promising correlation between the linear rheological results and the morphological features of the synthesized PP reactor blends.

Enhanced hydrophobicity of polyurethane via non-solvent induced surface aggregation of silica nanoparticles.

Fabrication of superhydrophobic surfaces from hydrophilic polymers has always been regarded as a challenge. In this study, to achieve superhydrophobic polyurethane (PU) surfaces, silica nanoparticles and ethanol as non-solvent were simultaneously utilized during a solution casting-based process. Such modified version of phase separation process was found to be highly efficient, and also it required much lower concentration of nanoparticles to achieve superhydrophobicity as compared to the previously reported methods in the literature. According to the proposed mechanism, non-solvent induces a more profound aggregation of silica nanoparticles at the surface's top layer causing the surface energy to be highly diminished, and thus, the water repellency is improved. Morphology and topography results showed that a unique "triple-sized" structure was formed on the surface of superhydrophobic samples. X-ray photoelectron spectroscopy results proved that both PU macromolecules and silica nanoparticles were concurrently present at the surface layer of the superhydrophobic sample. It was concluded that surface composition and roughness could be regarded as competing factors in achieving superhydrophobicity. Based on the obtained results, the proposed method exhibits a promising potential in large-scale fabrication of surface layers with superhydrophobic property. Moreover, a mechanism was also presented to further explicate the physics behind the suggested method.

Investigating the role of surface micro/nano structure in cell adhesion behavior of superhydrophobic polypropylene/nanosilica surfaces.

The main aim of the current study was to investigate the effects of different topographical features on the biological performance of polypropylene (PP)/silica coatings. To this end, a novel method including combined use of nanoparticles and non-solvent was used for preparation of superhydrophobic PP coatings. The proposed method led to a much more homogeneous appearance with a better adhesion to the glass substrate. Moreover, a notable reduction was observed in the required contents of nanoparticles (100-20 wt% with respect to the polymer) and non-solvent (35.5-9 vol%) for achieving superhydrophobicity. Surface composition and morphology of the coatings were also investigated via X-ray photoelectron spectroscopy and scanning electron microscopy. Based on both qualitative and quantitative evaluations, it was found that the superhydrophobic coatings with only nano-scale roughness strongly prevented adhesion and proliferation of 4T1 mouse mammary tumor cells as compared to the superhydrophobic surfaces with micro-scale structure. Such results demonstrate that the cell behavior could be controlled onto the polymer and nanocomposite-based surfaces via tuning the surface micro/nano structure.